1、 CH2O(11)ACHCHHOCPha|223CHCHCHOCPho223CH3CH3(12)OOOOpnuch2ch2一c一PhfPhCCHCHCPh2.在下列指定原料和產(chǎn)物的反應(yīng)式中分別填入必需的化學(xué)試劑（或反應(yīng)物）和反應(yīng)條件。（參考答案）題號(hào)答案注釋11.KMnO4,H20;2.HC12CrO3(Py)2J.Org.Chem.,1969,34:1979.3CrO3(Py)2J.Org.Chem.,1969,34:3587.4CrO3(Py)2J.Org.Chem.,1979,44:2441.5DMSO,Ac2O6Org.Lett.,2003,5:3049.7Ag2O8J.Org.Che

2、m.,1992,57:6696.9CH3COOOH,NaHCOqJ.Org.Chem.,1987,52:4898.10KMnO4,H2O,5C111.O3;2.Zn,H2OJ.Org.Chem.,1972,37:2877.12SeO,80%AcOH、(aq_)3.閱讀(翻譯)以下有關(guān)反應(yīng)操作的原文，請(qǐng)?jiān)诶斫饣A(chǔ)上寫出：(1)此反應(yīng)的完整反應(yīng)式(原料、試劑和主要反應(yīng)條件)；(2)此反應(yīng)的反應(yīng)機(jī)理(歷程)。Dipyridinechromium(VI)oxide(Note1).Adry,1-l.,three-neckedflaskfittedwithasealedmechanicalstirrer,

3、athermometer,andadryingtube,ischargedwith500ml.ofanhydrouspyridine(Note2),whichisstirredandcooledtoapproximately15(Note3)withanicebath.Thedryingtubeisperiodicallyremovedand68g.(0.68mole)ofanhydrouschromium(VI)oxide(Note4)isaddedinportionsthroughtheneckoftheflaskovera30-minuteperiod.Thechromiumtrioxi

4、deshouldbeaddedatsucharatethatthetemperaturedoesnotexceed20andinsuchamannerthattheoxidemixesrapidlywiththepyridineanddoesnotadheretothesideoftheflask(Note5).Asthechromiumtrioxideisadded,anintenselyyellow,flocculentprecipitateseparatesfromthepyridineandtheviscosityofthemixtureincreases.Whentheadditio

5、niscomplete,themixtureisallowedtowarmslowlytoroomtemperaturewithstirring.Withinonehourtheviscosityofthemixturedecreasesandtheinitiallyyellowproductchangestoadeepred,macrocrystallineformthatsettlestothebottomoftheflaskwhenstirringisdiscontinued.Thesupernatantpyridineisdecantedfromthecomplexandthecrys

6、talsarewashedseveraltimesbydecantationwith250-ml.portionsofanhydrouspetroleumether.Theproductiscollectedbyfiltrationonasinteredglassfunnelandwashedwithanhydrouspetroleumether,avoidingcontactwiththeatmosphereasmuchaspossible.Thecomplexisdriedat10mm.untilitisfree-flowing,leaving150-160g.(8591%)ofdipyr

7、idinechromium(VI)oxide3asredcrystals.Theproductisextremelyhygroscopic;contactwithmoistureconvertsitrapidlytotheyellowdipyridiniumdichromate.4Itisstoredat0inabrownbottle(Note6).Generaloxidationprocedureforalcohols.Asufficientquantityofa5%solutionofdipyridinechromium(VI)oxide(Note1)inanhydrousdichloro

8、methane(Note7)ispreparedtoprovideasixfoldmolarratioofcomplextoalcohol,anexcessusuallyrequiredforcompleteoxidationtothealdehyde.Thefreshlyprepared,purecomplexdissolvescompletelyindichloromethaneat25at5%concentration,givingadeepredsolution,butsolutionsusuallycontainsmallamountsofbrown,insolublemateria

9、lwhenpreparedfromcrudecomplex(Note8).Thealcohol,eitherpureorasasolutioninanhydrousdichloromethane,isaddedtotheredsolutioninoneportionwithstirringatroomtemperatureorlower.Theoxidationofunhinderedprimary(andsecondary)alcoholsproceedstocompletionwithin5to15minutesat25withdepositionofbrownish-black,poly

10、meric,reducedchromium-pyridineproducts(Note9).Whendepositionofreducedchromiumcompoundsiscomplete(monitoringthereactionbyGCorTLCishelpful),thesupernatantliquidisdecantedfromthe(usuallytarry)precipitate,whichisrinsedthoroughlywithdichloromethane(Note10).Thecombineddichloromethanesolutionsmaybewashedwi

11、thdilutehydrochloricacid,sodiumhydrogencarbonatesolution,andwater,orfiltereddirectlythroughafilteraid,orpassedthroughachromatographiccolumntoremovetracesofpyridineandchromiumsalts.Theproductisobtainedbyremovalofdichloromethane;anypyridinethatremainscanoftenberemovedunderreducedpressure.Heptanal.Adry

12、,1-l.three-neckedround-bottomedflaskisequippedwithamechanicalstirrer,and650ml.ofanhydrousdichloromethane(Note7)isadded.Stirringisbegunand77.5g.(0.300mole)ofdipyridinechromium(VI)oxide(Note1)isaddedatroomtemperature,followedby5.8g.(0.050mole)of1-heptanol(Note11)inoneportion.Afterstirringfor20minutes,

13、thesupernatantsolutionisdecantedfromtheinsolublebrowngum,whichiswashedwiththree100-ml.portionsofether.Theetheranddichloromethanesolutionsarecombinedandwashedsuccessivelywith300ml.ofaqueous5%sodiumhydroxide,100ml.of5%hydrochloricacid(Note12),two100-ml.portionsofsaturatedaqueoussodiumhydrogencarbonate,and,finally,with100ml.ofsaturatedaqueoussodiumchloride.Theorganiclayerisdriedoveranhydrousmagnesiumsulfate,andthesolventisremovedbydistillation.DistillationoftheresidualoilatreducedpressurethroughasmallClaisen